Fluorine-containing alcohols and process for preparing the same



Patented July 10, 1951 FLUORINE-CONTAINING ALCOHOLS AND PROCESS FOR PREPARING THE SAME Robert M. Joyce, Jr., Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmingto n, DeL, a corporation of Delaware .No Drawing. Application December 13, 1948, Se-

rial No. 65,063. In Canada April 22, 1944 14 Claims. (01. 260633) This invention relates to new organic fluorine compounds and to methods for their preparation. More particularly this invention relates to new fluorine-containing alcohols and to processes for preparing them.

This invention is a continuation-in-part of my copending application Serial No. 567,777 filed December 11, 1944, and now abandoned which is a continuation-in-part of application Serial No. 484,300 filed April 23, 1943, and which is now abandoned.

Much work has been directed toward developing a good method for preparing highly fluorinated organic compounds. It has previously been proposed to produce organic fluorine compounds by the reaction of fluorine with various organic materials. Prior investigations have shown that this reaction of fluorine is extremely energetic and generally causes pyrolysis of the organic material, resulting in the formation of carbon, tar or other undesirable carbonaceous decomposition products.

Heretofore, the only practical method for preparing fluorine-containing organic compounds has been to replace chlorine or bromine with fluorine by means of various inorganic reagents, such as hydrogen fluoride, silver fluoride, antimony fluorides, mercuric fluoride and other metallic fluorides. However, such processes involve considerable expense and are very restricted in application.

It is an object of this invention to provide new compositions of matter consisting of fluorine-containing alcohols and methods for their preparation. A further object is to provide fluorine-containing alcohols which have extreme stability and inertness. A still further object is to provide fluorine-containing alcohols possessing many novel and useful properties. Another object is to provide relatively simple and inexpensive processes for obtaining new fluorine-containing alcohols. Other objects will appear hereinafter.

These and other objects and advantages are accomplished by providing new fluorine-containing alcohols having from one to twelve completely halogenated polyfluoroethylene groups per molecule. The new products of this invention are the reaction products of a tetrahaloethylene wherein the four halogen atoms have an atomic weight of less'than 40, and at least two of them are fiuorineatoms, with an alcohol which contains a non-aromatic carbon atom'bearing a hydroxyl group and a. hydrogen atom directly attached thereto and in which all of the nonaromatic carbonatoms are saturated, the reaction product having a hydroxyl group and containing from one to twelve of said tetrahaloethylene units. These new fluorine-containing alcohols are represented by the formula wherein the X substituents are halogen atoms having an atomic weight of less than 40 ,of which at least half in each CXzCXz group are fluorine atoms, n is a positive integer from 1 to 12 and ZOH is the radical of a non-tertiary alcohol which contains a non-aromatic carbon atom directly attached to the hydroxyl group and in which all of the non-aromatic carbon atoms are saturated.

The preferred tetrahaloethylene is tetrafluoroethylene and the new fluorine-containing alcohols resulting therefrom are represented by the formula H(CF2CF2)ZOH where n and ZOH are defined as aforesaid. The preferred class of alcohols are primaryand secondary hydrocarbon are represented by the formula H(CX2CX2) ,iROH' where X and n are defined as aforesaid, R is a divalent hydrocarbon radical, preferably 7 a divalent saturated aliphatic hydrocarbon radical, and ROH is the radical of a non-tertiary alcohol. Thus ROH is the monovalent radical of a primaryor secondary alcohol, that is themonovalent radical of a nop tertiary' alcohol. The preferred new fluorine-containing alcohols have the formula H(CF2CF'2) nR-OH where n, R and ROI-l are defined as aforesaid. Particularly preferred fluorine-containing alcohols have the formula H(CF2CF2)1;ROH where'n is a positive integer from 1 to 12, R is a divalent saturated open-chain aliphatic hydrocarbon radical containing from 1 to 6 carbon atoms and ROH is a saturated open-chain aliphatic radical of a monohydric non-tertiary alcohol.

The novel product-sot this invention can be prepared by heating at a temperature of to 350 C. in thepresence of a catalyst a completely halogenated fluoroethylene having theformula CXsCXz containing at least two fluorine atoms, the remaining halogen atoms, if any. being chlorine atoms, with an alcohol which is free of non-aromatic unsaturation and in which the carbon atom bearing the hydroxyl group has directly attached thereto a hydrogen atom, i, e.,

' a primary or secondary alcohol.

3 from non-aromatic unsaturation. preferably in a closed system and in the presence of a peroxy or azo catalyst. There are thus obtained saturated polyfluoro organic compounds which contain alcoholic hydroxyl groups and which contain one or more tetrafluoroethylene units per molecule of alcohol.

By the expression organic compound tree rrom non-aromatic unsaturation, as used herein and in the appended claims, is meant an organic compound which is free from carbon to carbon multiple bonds, i. e., a double or triple bond 'linking two adjacent carbon atoms. other than those which are present in somatic ring, e. g., a benzene nucleus.

The method for carryin out the reactions varies to some extent with diflerent alcohols, but the usual procedure comprises placing the reactants in a stainless steel or silver-lined high pressure reaction vessel and then closing and heating to the desired reaction temperature while mechanically agitating the reaction vessel for the reaction period.

In order to prepare the low molecular weight products which are characteristic of this invention, it is usually desirable to carry out the reaction under pressure at elevated temperatures. The temperature at which the reaction is elected may be varied over a wide range, depending largely upon the nature of the reactants. the catalyst, the results desired and other conditions of the reaction. However, the temperature should be below that at which decomposition or pyrolysis of either the reactants or products occurs. With peroxy catalysts. no appreciable reactionis obtained below 75 C. and it is usually necessary to heat the reaction mixture to about 100 C. or higher in order to obtain a substantial reaction in a reasonable time. temperature range with peroxy catalysts is 100 to 250 C. but temperatures high as 350' C. are sometimes desirable. However, with azo catalysts temperatures. as low as 50 C. may be employed, suitable temperatures being 60 to 200 C.

A series of products can be obtained which vary from liquids to solids depending upon the number oi! fluoroethyiene-units per molecule. The products are highly fluorinated saturated alcohols containing one or more units of the fluoroethylene per molecule. The products vary from liquids which are compatible with the common organic solvents to solids which are soluble in selected solvents. such as acetic acid.

The invention is further illustrated by'the following examples in which proportions are in parts by weight unless otherwise specified.

Example I One hundred and twenty parts of methanol and 1.5 parts of diethyl peroxide were charged into a stainless steel autoclave. The autoclave was cooled. evacuated and 50 parts of tetraiiuoroethylene added. The autoclave was closed and heated at 175 C. for 8 hours. The reaction mixture was steam distilled to yield 6.9 parts of steam-volatile liquid products insoluble in and heavier than water, 2.5 parts of steam-volatile solid which contained an average of about five tetratiuoroethylene units/methanol unit, and 17.4 parts of nonsteam-volatile solid wherein the number of tetrafluoroethyiene units/methanol unit ranged up to about twelve (M. P. about 279 C.). The liquid products were iractionally distilled through an emcient column to give fractions correpponding to the 1:1 (Cal's/CECE) The preferred assaoss- 1' Pet 0 Pa- K Per Cent Oent Cent Found 63. 00 24. 18 l. 25 Calculated for H(CF,CF)1CH|OH 65. 4 25. 1.72 Calculated for H(CF|CF;):CH;OH B8. 5 25. 30 l. I)

Esteriilcation of a low molecular weight liquid reaction product obtained having a boiling range of 145-170 C. with acetic anhydride gave the acetate F Per Molecular Cent Weight Found..-. 54.51 m Calculated for H(CFgOF;),CHiOC-CH|. 55. 4 274 Example 1! One hundred and twenty parts 01 isopropanol. 1.5 parts of benzoyl peroxide and 50 parts of tetrafluoroethylene were heated 9.5 hours at C. under pressure. Steam distillation of the reaction mixture yielded 18 parts of water-insoluble liquid which was heavier than water and 0.5 part of nonsteam-volatile waxy pellets (M. P. about 250 C.). Fractionation of the volatile liquid products yielded a series of liquids which increased in percentage of fluorine with increase in boiling point from the 1:1 product boiling around C. to products boiling above 200 C. at atmospheric pressure which contained more than 3 tetrafluoroethylene units to one isopropanol unit. These liquid products react with metallic sodium giving of! hydrogen and can be esterifledby reacting with acetic anhydride to yield esters.

Boillngjioint, Analysis, Calculated, Ratio F Per Cent F Per Cent CzlN/CflhO A similar reaction was obtained using secondary butanol instead of isopropanol.

Example III A mixture of 150 parts of methanol and 2 parts of 1.l'-azodicyclohexanecarbonitrile was placed in a high pressure reactor having a capacity of 400 parts by volume under an atmosphere oi nitrogen. The reactor was closed, cooled and 110 parts of tetrafluoroethylene was distilled in through a valve. The reactor was then agitated and heated at C. for 10 hours under autogenous pressure. The crude reaction product was subjected to steam distillation, whereby 20 parts or steam-volatile mixed liquid and solid distilled and a residue oi! 18 parts remained. The steam-volatile portion was separated into liquid and solid fractions and the liquid fraction was dried and distilled. yielding 10 parts boiling in the range -200 C. and leaving a residue of 7 parts which solidified vfraction was a mixture of compounds y on cooling. The liquid H(CF CFz),-CH2OH in which n is 2 and 3 and the solid residue was a mixture of similar compounds in whichn has the values 1 and 5. The steam-volatile solid fraction was recrystallized from chloroform yielding 1.5 parts of the compound mcracrmcmon,

melting at125-129 c. Example IV H (CF2CF2) nCHllOH The solid steam-volatile fraction was recrystallized from chloroform to give 17.5 parts of the compound in which 1:. equals 6 and a second fraction, parts, in which n equals '5. vThe filtrate from the recrystallization was evaporated and distilled to give 18 parts of a mixture of the compounds in which n equals 4 and 5..

' A portion of the reaction product not volatile with steam was subjected to fractional vacuum sublimation, yielding two fractions. After puriflcation by resublimation, these fractions melted at 155-160 C. and 185-490 C., respectively, and

were identified as the compounds H (CF2CF2) nCHZOH in which n is 7 and 8.

Still longer chain alcohols were obtained by exhaustive methanol extraction of the remainder of the non-steam-volatile reaction product. This extraction served to remove short chain alcohols, including the alcohol in which n is 8, which is methanol-soluble. The residue from this extraction was a mixture of alcohols which melted over the range 200-280 C. The highest melting '(280 C.) compound in this mixture corresponds,

onthe basis of the regularities in the melting points of the lower members of the series, to the compound H(CF2CF2)12CH2OH. The properties of these compounds are summarized in the following table.

l iCF2)nCH2OH] Per Cent F 1| B. P M. P

Cale. Found Degrees 2 65. 4 64.1 3 68. 6 ass 4 65- 67 70.4 70. 1 5 95- 97 71. 4 71. 6 6 129-130 72.1 71.3 7 155-160 72.6 x 3 185-190 73.0 (i) 12 74.0 x

1 Fluorine analyses were not made on these compounds because of the slight differences in fluorine content.

The presence of hydroxyl groups in these compounds was established by absorption bands at 3 in their infrared spectra. The structures of rep- 6 resentative' iractions were further confirmed by,

oxidation to the corresponding acids which had the correct neutral equivalents.

Example V I Amixture of 150 parts of ethanol and 5 parts of l,l'-azobis(l-phenylethane was charged into a high pressure reactor having a capacity of 400 parts of water by volume. The reactor was closed, cooled, and 110. parts of tetrafiuoroethylene was distilled in through a valve. The reac tor was then agitated and heated at 175 C. for 8 hours under autogenous pressure. There was obtained 220 parts of clear yellow liquid product.

Preliminary distillation of this product to remove the ethanol left a residue of 45 parts which was subjected to careful fractional distillation.

There were obtained two principal fractions boiling at and C. These correspond to the compounds H(CF2CF2)nC2H4OH, in which n is 1 and 2, respectively. The analytical data for these compounds are as follows:

Per Cent Fluorine B. P n

. Calc. Found Degrees The presence of hydroxyl groups in these compounds was confirmed by absorption bands at 311. in their infrared spectra.

Example VI A mixture of parts of isopropyl alcohol and 5 parts of '1,1-azobis(1-phenylethane) was charged into a high pressure reactor having a capacityof 400 parts by volume. The reactor was closed, cooled, and 110 parts of tetrafluoroethylene was distilled in through a valve. The

reactor was then agitated and heated at C. for a period of 8 hours under autogenous pressure. There was obtained 250 parts of clear liquid which was subjected to steam distillation. There was obtained 87 parts of liquid fraction to which was added an additional 10 parts which was salted out of the aqueous steam distillate with potassium carbonate. This liquid was dissolved in 25 parts of chloroform, dried over potassium carbonate, filtered and distilled. There were obtained three principal fractions boiling at 120, 150, and 183 C. These fractions correspond to the compounds H(CF2CF2)nC3H6OH, in which n is 1, 2 and 3 respectively. The analytical dat for these fractions are as follows:

- Per Cent Fluorine B. P. 1|

Calculated Found Degrees The presence of hydroxyl groups in these compounds was confirmed by absorption bands at 3,1. in their infrared spectra.

Example VII A mixture of 100 parts of methanol and 5 parts of alpha,alpha'-azodiisobutyronitrile was placed parts or distillate. The residue was then distilled at 110-130 C. at 4 mm. pressure to give 5 parts ota mixture of yellow liquid and solid. This 5-part distillate was dissolved in 50 parts of glacial acetic acid, and parts of potassium perto was added slowly to the refluxing solution. After the addition was complete andthe resulting sludge had been refluxed several minutes, sulfur dioxide was bubbled in until the solution became clear. After evaporation to drynesson a steam bath at 2 mm. pressure, the residual salt'mixture was'washed with 25 parts of toluene. The residue was then washedwith parts oi water. The filtrate was acidified with concentrated sulfuric acid. The acidic two-layer solution was then extracted with two -part portions of ether and the ether extracts combined, dried, and distilled to give besides the ether, (a) 1 part oi. clear liquid boiling at 42 C. at '45 mm. and (b) 0.5 part 0! yellow oil boiling at 100-13090. at 3 mm. The neutral equivalents oi! these acids were:

(a) AnaL: Calcd for H(C2F:Cl) COzH- Neutral Equiv.; 182.5

Found-Neutral Equiv.; 145.7 (b) AnaL: Calc'd for H(Cz1"aCl):COsH-- Neutral Equiv.; 395.5 PoundN eutral Equiv.; 414.7

Fraction b corresponds to the I-carbon acid H(C:F:CI):CO:H contaminated with a little of the higher acid H(C2F:C1)4CO:H. The original reactbn products of methanol and chlorotrifluoroethylene therefore have the corresponding structure H(C21C1)3CH2OH where n is l, '2, 3

. non-aromatic unsaturation.

Among the completely halogenated fluoroethylenes which are operative in the process of this invention are tetrafluoroethylene, 'chlorotrifluoroethylene, i,l-dichloro-2,2 ditluoroethylene and 1,2-dichloro-L2-difluoroethylene. The process is particularly applicable to tetrafluoroethylene which reacts the most readily and is therei'ore preferred.

' While all primary and secondary alcohols which are free of non-aromatic unsaturation, i. e., ethylenic and acetylenic linkages, are operative in my novel process, products having the most desirable properties are produced when the alcohol reacted is a primary or secondary saturated aliphatic alcohol. Primary and secondary alcohols which are operative include acyclic and cyclic, including aliphatic, alicyclic, heterocyclic and aralkyl alcohols. The alcohols may be monohydric, polyhydric or polymeric. Included among examples of such alcohols are aliphatic alcohols. such as methyl alcohol, ethyl alcohol, n-propyl 8 alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, octyl alcohol, lauryl alcohol and 'stearyl alcohol: cycloaliphaticalcohols, such as cyclohexyl alcohol and methyl cyclohexyl alcohol; hetcrocyclic alcohols such as tetrahydroiuriuryl alcohol; aralkyi alcoholsrsuch as benzyl alcohol and 'phenyleth'yl alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerol hexametliyiene glycol, decamethylene glycol, mannitoi and sorbitol; polymeric alcohols, such as polyvinyl alcohol. Alcohols containing functional groups in addition to the alcoholic hydroxyl group are also operative. These include the halohydrins, such as ethylene chlorohydrin, ethylene bromohydi'in and glycerol chlorohydrin; hydroxyacetic' acid and its esters; the monomethyl-, monoethyland monobutyl ethers oi ethylene glycolfand the higher polyethylene glycols and their ethers and esters, such. as the monoacetate of ethylene glycol.

Although a mixture of alcohols, as hereinbeiore defined, can be reacted with completely halogenated fluoroethylene in accordance with this invention, it is preferable to react asingle alcohol therewith. Generally. a relatively large molar excess oi the alcohol is used as compared to the fluoroethylene in order to prepare low molecular weight products. However, the desired products may often be obtained by using a relatively small amount of said alcohol depending upon the reaction conditions. Usually the molar ratio oi said alcohol to fluoroethylene in thereaction mixture may vary from about 0.04:1 to 20:1, but the desired low molecular weight products are obtained in highest yield when said ratio is within the range of from 1:1 to 10:1,

Organic and inorganic peroxy compounds and oxygen are operative in my invention. Included among examples of said catalysts are: diacyl peroxides, such as benzoyl peroxide and lauroyl peroxide; alkyl peroxides, such as diethyl peroxide and tertiary butyl hydroperoxide; inorganic peroxides, such as hydrogen peroxide; salts of peracids, such as ammonium persuli'ate, sodium perborate and potassium percarbonate; oxygen; ozone and the like.

Azo catalysts are also operative to produce the fluorine-containing alcohols of my invention. Included among examples of said azo catalysts are: carbamylazoisobutyronitrile, alpha, alphaaaodiisobutyronitrile, alpha, alpha'-aaobis (alpha,

gamma-dimethylvaleronitrile), alpha, alphaazobis (alpha-phenylpropionitrile), alpha, alpha'-azobis (alpha, gamma-dirnethyl-gammamethoxyvaleronitr'ile) 1,l-azodicyclohexanecarbonitrile, alpha, alpha'-azo-diisobutyramide, and dimethyl alpha, alpha'-azodiisobutyrate. These compounds may be prepared by the methods 0! Thiele and Heuser, Ann. 290, 1-43 (1896), or

vI-Iartmann, Rec. trav. chim. 46, -153 (1927).

The proportion of catalyst may vary within relatively wide limits depending largely upon the nature of the reactants and the products desired. Highly desirable results are obtained with the use of 1 catalysts corresponding to an amount within the range of from 0.001 to 10% by weight of the reactants employed. Advantageous results are sometimes obtained by using a combination of catahrsts.

It will be understood that the operating conditions may vary widely depending upon the nature of the reactants and also upon the result desired. In general, the reaction is eflected under substantially anhydrous conditions. The time reassaosa 9 quired for carrying out the reaction-may vary from aufew. minutes to several daysdepending upon the nature of the reactants and the other operating conditions, such as temperature. pressure and catalyst.

The process may be operated continuously or intermittently. The reaction may be carried out in a closed system or the reaction may be carried out in the vapor phase by mixing the vapors of the alcohol and the fluoroethylene and passing the mixture of vapors through a hot reaction tube which if desired may contain a catalyst. In general, the reaction may be carried out under atmospheric or superatmospheric pressure in the range of 1 to 1000 atmospheres. The preferred pressure range is 1 to 200 atmospheres.

The reaction may be carried out in any suitable reaction vessel. such as stainless steel, iron. silver, aluminum, and other metals and alloys which are capable of withstanding heat and pressure. The reaction is preferably carried out with agitation, but agitation is not always necessary.

While this invention has beenillustrated with particular reference to the use of azo catalysts and peroxygen substances as catalysts, it is contemplated that any catalyst may be employed which yields free radicals under the reaction conditions. Particularly useful as catalysts are peroxygen and azo compounds which may be represented as having an open chain structure RXXR where X-X is either O-O- or N=N and R is preferably an organi radical.

The present invention is useful for the produc-. tion of a wide variety of organic fluorine compounds. Although it is understood that often a mixture of compounds with varying ratios of fluoroethylene units per molecule of alcohol is obtained, the mixture can generally be separated into definite fractions by various methods, such as steam distillation, fractional distillation, flltration, extraction, fractional -crystallization, or by chemical methods; A high yield of products having a 1:1 ratio of the fluoroethylene to the alcohol frequently can be obtained by using selected conditions.

The products of this invention prepared from tetrafluoroethylene have the general formula H(CFzCF2)'nZOH, wherein n is a positive integer ranging from onbito twelve and ZOH is the complementary portion of the alcohol, said alcohol being either primary or secondary and free from non-aromatic unsaturation.

The reaction involved in the preparation of the aforementioned compounds may be illustrated by the following specific equation:

mcr$=crt +CHaOH H(CFzCF2) onion wherein n is a positive integer within the range of from one to twelve.

In general, the reaction products contain a major proportion of compounds containing from 1 to about 5 fluoroethylene molecules chemically combined with one molecule of the alcohol.

The products can be distinguished readily from the polymerized fluoroethylene by their analysis, by their physical properties and often by their chemical reactions. The products of this invention vary from liquids to relatively low molecular weight solid products which soften or melt below 300 C. when heated in air on a copper block. The liquid products are generally compatible with the common organic solvents and considerable amounts of the solid products are soluble in acetic acid. The presence of the alcoholic hy droiq l in the products of this invention can often as bytheir absorption in the infra red.

The reaction andthe separation or isolation of the products may be carried out simultaneously orin separate steps. The products may be separated 'by filtration, extraction, distillation orcrystallization depending upon the nature of the products.

The products of this invention are useful for various commercial purposes. Since many of the products of this invention are extremely stable, they aregenerally applicable for use as solvents, reaction media, lubricants and idielectrics. Many of the products have been found to be very desirable in'that they are substantially non-flammable, non-corrosive and non-toxic. Substituted. fluorocarbons having outstanding thermal and chemical stability can be prepared according to the present invention. This invention is particularly advantageous in that it affords a safe, flexible, practical and economical method of producing highly fluorinated saturated alcohols. One of the advantages of the invention is that the process may beoperated with a relatively small amount of catalyst and the reaction proceeds smoothly and easily.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I .do not limit myself to the specific embodiments thereof except as defined in'the appended claims.

I claim:

L'The process for obtaining fluorine-containing alcohols, which comprises heating at a temperature within the range of from C. to 250 C. a haloethylene having the general formula:

wherein the X substituents are. halogen atoms having an atomic weight of less than 40 and at least two of said X substituents are fluorine atoms, with an alcohol which contains a nonaromatic carbon atom bearing a hydroxyl group and a hydrogen atom directly attached thereto and in which all of the non-aromatic carbon atoms are saturated, the mole ratio of said alcohol to said haloethylene being within the range of from 1:1 to 10:1, said heating being effected under a pressure within the range of from one atmosphere to 200 atmospheres and in the presence of an amout of peroxy catalyst. within the range of from 0.001% to 10% of. the combined weight of' said haloethylene and alcohol.

2. The process for obtaining organic fluorinecontaining alcohols, which comprises heating at a temperature within the range of from 100' C. to 250 C. a haloethylene having the general formula has a hydrogen atom directly attached thereto, the mole ratio of said alcohol to said haloethylone being within the range 01 from 1:1 to 10:1, said heating being elected under a pressure within the range oi from one atmosphere to'200 atmospheres and in thepresence oi an amount oi peroxy catalystwithin the'rangeot from 0.001% to 10% oi the combined weight of said haloethylene and alcohol.

organic fluo- 8. The process for obtaining fine-containing alcohols. which comprises heating at a temperature within the range oi from 100C. to 250' C. tetraiiuoroethylene with a saturated monohydric aliphatic alcohol which contains from one to six carbonatoms'and in which the carbon atom bearing the hydroxyl group has at least one hydrogen atom directly attached thereto, the mole ratio 01' said alcohol to said tetraiiuoroethylene being within the range of from 1:1 to 10:1, said heating being'eitested under a pressure within the range of from one atlnbosphere to 200 atmospheres and in the presence of an amount of peroxy catalyst within the range of from 0.001% to 10% ot the combined weight of said tetrafluoroethylene and alfrom 1:1 to 10:1, said heating being eiiected un-- der a pressure within the range of from one atmosphere to 200 atmospheres in the presence of an amount of diethyl peroxide within the range of irom'0.001% to 10% of the combined weight of said tetraiiuoroethylene and methanol.

5. The process for obtaining organic fluorine-containing alcohols which comprises heating tetrailuoroethylene with isopropanol at a temperature within the range of from 100 C. to 350 6., the mole ratio of said isopropanol to said tetrailuoroethylene being within the range of from 1:1 to 10:1, said heating being eilected underapressurewithin therange of from one atmosphere to 200 atmospheres in the presence of an amount oi bensoyl peroxide within the range of from 0.001% to 10% oi the combined weight of said terafluoroethylene and isopropanol.

' 0. A saturated fluorine-containing alcohol melting below 800 C. and having the formula mcxaxnmon where n is a positive integer from 1 to 12, the substituents are halogen atoms having an atomic weight 01 less than 40 of which at least half in each CXzCX: group are fluorine atoms, R is a divalent hydrocarbon radical and R03 is a monovalent radical of a nontertiary alcohol which contains a non-aromatic carbon atom bearing the alcoholic hydroxyl group and in which all oi the non-aromatic carbon atoms are saturated.

7. A saturated fluorine-containing alcohol melting below 300 C. and having the formula H(CX:CX:);ROH where n is a positive integer from 1 to 12, the 1: substituents are hal g n 12 atoms having an atomic weight at less than 40 ct which at least halt ineach cx=cx= group are fluorine atoms. R is a divalent saturated aliphatic hydrocarbon radical and R011 is 'a monovalent radical of a saturated aliphatic non-tertiary alcohol.

8. A saturated fluorine-containing alcohol melting below 800' C. and having the formula H(Cl"aCF:)aRQH"where n is a positive integer from 1 to 12. R is a divalent aliphatic hydrocarbon radical and R08 is a monovalent radical 01' a saturated aliphatic non-tertiary alcohol. L

9; A saturated fluorine-containing alcohol melting below 300 C. and having the formula H(C1":CI":).ROH where n is a positive integer from 1 to 12, R is a divalent saturated openchain aliphatic radical and ROH is a monovalent radical of a saturated open-chain aliphatic primary alcohol.'

10. A saturated fluorine-containing alcohol melting below 300- c. and havingthe lormula mcrscrmnzon where n is a positive integer from 1 to 12, R is a divalent hydrocarbon radical and 80K is a monovalent radical 0! a nontertiary alcohol which contains a non-aromatic carbon atom bearing the hydroxyl' group and in which all 0! the non-aromatic carbon atoms are saturated.

11. A saturated fluorine-containing alcohol melting below 300 C. and having the formula H(CI":CF:);ROH where n is a positive integer from 1 to 12 andRisadivalentsamratedopenchain aliphatic hydrocarbon radical containing from 1to6carbonatomsandROHisamonovalent radical of a saturated open-chain aliphatic non-tertiary alcohol. 1

12. A saturated fluorine-containing alcohol melting below 300 C. and having the formula H(CF5CI":) aCHzOH where n is a positive integer 13. A saturated fluorine-containing alcohol melting below 300 C. and having the formula H(CF:C1":) .CaHqOH where n is a positive integer from 1 to 12.

14. A saturated fluorine-containing alcohol melting below 300 C. and having the formula 3(01'501'5) Cali-OH where n is a positive integer from 1 to 12. I

ROBERT M. JOYCE, Jl.

Theiollowingreierencesareofrecordinthe lileotthispatent:

UNITED STATE PATENTS Number Name Date 2,230,654 Plunkett Feb. 4, 1941 2,411,159 Haniord Nov. 19, 1946 Compt. Rend. Acad. Sci. vol 55. mes 223-6 (1947) (Knunyants) Abstracted in Chemical Abstracts, vol. 41, (1947). pm 5855a. 

1. THE PROCESS FOR OBTAINING FLUORINE-CONTAINING ALCOHOLS, WHICH COMPRISES HEATING AT A TEMPERATURE WITHIN THE RANGE OF FROM 100* C. TO 250* C. A HALOETHYLENE HAVING THE GENERAL FORMULA:
 6. A SATURATED FLUORINE-CONTAINING ALCOHOL MELTING BELOW 300* C. AND HAVING THE FORMULA H(CX2CX2)NROH WHERE N IS A POSITIVE INTEGER FROM 1 TO 12, THE X SUBSTITUENTS ARE HALOGEN ATOMS HAVING AN ATOMIC WEIGHT OF LESS THAN 40 OF WHICH AT LEAST HALF IN EACH CX2CX2 GROUP ARE FLUORINE ATOMS, R IS A DIVALENT HYDROCARBON RADICAL AND ROH IS A MONOVALENT RADICAL OF A NONTERTIARY ALCOHOL WHICH CONTAINS A NON-AROMATIC CARBON ATOM BEARING THE ALCOHOLIC HYDROXYL GROUP AND IN WHICH ALL OF THE NON-AROMATIC CARBON ATOMS ARE SATURATED. 